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WO2012077929A2 - Matériau de cathode et batterie secondaire utilisant ledit matériau - Google Patents

Matériau de cathode et batterie secondaire utilisant ledit matériau Download PDF

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Publication number
WO2012077929A2
WO2012077929A2 PCT/KR2011/009169 KR2011009169W WO2012077929A2 WO 2012077929 A2 WO2012077929 A2 WO 2012077929A2 KR 2011009169 W KR2011009169 W KR 2011009169W WO 2012077929 A2 WO2012077929 A2 WO 2012077929A2
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WO
WIPO (PCT)
Prior art keywords
negative electrode
active material
carbon
group
secondary battery
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/KR2011/009169
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English (en)
Korean (ko)
Other versions
WO2012077929A3 (fr
Inventor
장성균
장원석
김제영
한정민
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LG Chem Ltd
Original Assignee
LG Chem Ltd
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Publication date
Application filed by LG Chem Ltd filed Critical LG Chem Ltd
Priority to EP11847200.0A priority Critical patent/EP2650953B1/fr
Priority to PL11847200T priority patent/PL2650953T3/pl
Priority to CN201180058590.8A priority patent/CN103250284B/zh
Publication of WO2012077929A2 publication Critical patent/WO2012077929A2/fr
Publication of WO2012077929A3 publication Critical patent/WO2012077929A3/fr
Priority to US13/904,588 priority patent/US8974962B2/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B60L50/60—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells using power supplied by batteries
    • B60L50/64—Constructional details of batteries specially adapted for electric vehicles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L50/00—Electric propulsion with power supplied within the vehicle
    • B60L50/50—Electric propulsion with power supplied within the vehicle using propulsion power supplied by batteries or fuel cells
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B60—VEHICLES IN GENERAL
    • B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
    • B60L58/00—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles
    • B60L58/10—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries
    • B60L58/18—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries of two or more battery modules
    • B60L58/21—Methods or circuit arrangements for monitoring or controlling batteries or fuel cells, specially adapted for electric vehicles for monitoring or controlling batteries of two or more battery modules having the same nominal voltage
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/60—Other road transportation technologies with climate change mitigation effect
    • Y02T10/70—Energy storage systems for electromobility, e.g. batteries

Definitions

  • the present invention relates to a negative electrode active material and a secondary battery using the same, and more particularly, to a secondary battery negative electrode active material capable of occluding and releasing ions, a core including a crystalline carbon-based material, and low crystallinity. At least one material selected from the group consisting of carbon and amorphous carbon and a composite coating layer (composite coating layer) comprising a hydrophilic material, the composite coating is at least one material selected from the group consisting of low crystalline carbon and amorphous carbon
  • the present invention relates to a negative electrode active material having a structure in which a filler consisting of a remaining component is contained in a matrix composed of one component selected from a hydrophilic material, and a secondary battery including the negative active material.
  • the lithium secondary battery has a structure in which a non-aqueous electrolyte containing lithium salt is impregnated in an electrode assembly having a porous separator interposed between a positive electrode and a negative electrode on which an active material is coated on a current collector.
  • Lithium cobalt oxide, lithium manganese oxide, lithium nickel oxide, lithium composite oxide, etc. are used as a positive electrode active material of such a lithium secondary battery, and carbon materials are mainly used as a negative electrode active material, and silicon compounds, sulfur compounds, etc. Use is also considered.
  • lithium secondary batteries have various problems, some of which are related to the manufacturing and operating characteristics of the negative electrode.
  • the carbon material used as a negative electrode active material exhibits a large hydrophobicity, and thus has low compatibility with the hydrophilic solvent in the preparation of the slurry for electrode preparation, resulting in poor uniform dispersibility of the solid components.
  • the hydrophobicity of the negative electrode active material makes it difficult to impregnate the electrolyte having a high polarity in the battery manufacturing process, the electrolyte impregnation process acts as a bottleneck section of the battery manufacturing process greatly reduces the productivity.
  • the carbon-based negative electrode active material is a solid electrolyte interface (SEI) layer is formed on the surface of the negative electrode active material during the initial charge and discharge (activation process),
  • SEI solid electrolyte interface
  • the electrolyte capacity is depleted during the collapse and regeneration of the SEI layer in the continuous charge and discharge process has a problem that the battery capacity is reduced.
  • the present invention aims to solve the problems of the prior art as described above and the technical problems that have been requested from the past.
  • the negative electrode active material for secondary batteries according to the present invention is a negative electrode active material for secondary batteries that can occlude and release ions
  • a core comprising a crystalline carbon-based material, and a composite coating layer comprising a hydrophilic material and at least one material selected from the group consisting of low crystalline carbon and amorphous carbon,
  • the composite coating has a structure in which a filler composed of the remaining components is contained in a matrix composed of one or more materials selected from the group consisting of low crystalline carbon and amorphous carbon, and one component selected from hydrophilic materials. consist of.
  • the negative electrode active material in which the composite coating layer having a matrix / filler structure including at least one material selected from the group consisting of low crystalline carbon and amorphous carbon and a hydrophilic material is coated on the core including the crystalline carbon material With such specific active material structures and components, the problems raised in the prior art can be solved at once.
  • the hydrophilic material included as a matrix or filler component in the composite coating layer exhibits high affinity with the hydrophilic solvent in the slurry for preparing the negative electrode to improve the dispersibility of solids in the slurry. Therefore, when the slurry is applied to the current collector to produce a negative electrode, distribution uniformity between components such as a binder and the negative electrode active material can be improved, and thus excellent electrode characteristics can be obtained.
  • the improvement of the uniformity by the hydrophilic material can minimize the weakening of the bonding strength with the partial current collector which appears in the non-uniform electrode, and basically the hydrophilic material increases the affinity with the current collector surface, By improving the bonding force, the problem of increase in internal resistance due to separation of the active material layer and the current collector is also solved.
  • the hydrophilic material included in the composite coating layer imparts hydrophilicity to at least a portion of the negative electrode active material, thereby greatly shortening the impregnation time of the polar electrolyte during the electrode manufacturing process, thereby significantly improving the productivity of the battery.
  • the hydrophilic material included in the composite coating layer has the same function as SEI having a strong chemical bond on the surface of the cathode and forms a layer having a stronger bond in advance, thereby reducing the amount of irreversible ions required for forming the SEI layer.
  • the at least one material selected from the group consisting of low crystalline carbon and amorphous carbon contained in the matrix or filler component in the composite coating layer minimizes the problem of lowering the electrical conductivity caused by the inclusion of the hydrophilic material. Furthermore, since the crystalline carbon-based material as a core has a potential close to lithium, dendrite growth of lithium tends to occur in the case of lithium secondary batteries, but one selected from the group consisting of low crystalline carbon and amorphous carbon Since the above materials are coated on the surface of the crystalline carbon-based material, this can be suppressed.
  • the negative electrode active material according to the present invention includes a core including a crystalline carbon material, at least one material selected from the group consisting of low crystalline carbon and amorphous carbon, and one component selected from a hydrophilic material (for example, a composite coating layer having a structure in which a matrix composed of amorphous carbon) includes a filler composed of remaining components (eg, hydrophilic materials).
  • carbon-based materials such as natural graphite
  • a soft carbon having a layered graphite structure, a low crystalline graphite structure (a structure in which hexagonal honeycomb planes of carbon are arranged in layers). soft carbon, and these structures are classified as hard carbon mixed with amorphous portions.
  • the crystalline carbonaceous material of the core component of the present invention may be graphite, or a mixture of graphite and low crystalline carbon, and low crystalline carbon, amorphous carbon, or any of the composite coating layer components. It may be a mixture of.
  • the hydrophilic material which is another component forming the composite coating layer in the present invention, exhibits relatively high hydrophilicity and polarity with respect to at least one material selected from the group consisting of low crystalline carbon and amorphous carbon, and has an effect on operating characteristics of the battery.
  • the material does not have a negative effect, its kind is not particularly limited, and preferably, may be an oxide that does not react with lithium, a nitride that does not react with lithium, a carbide that does not react with lithium, and the like. These may be used alone or in the form of a mixture of two or more.
  • Preferred examples of the oxide include, but are not limited to, aluminum oxide, magnesium oxide, zirconium oxide, selective mixtures thereof, and the like.
  • nitride examples include, but are not limited to, silicon nitride.
  • carbides include silicon carbide, cobalt carbide, mixtures thereof, and the like, but are not limited thereto.
  • the structure of the composite coating layer may be classified according to which components the matrix and the filler are made of.
  • the first exemplary structure it may be a structure in which the filler of the hydrophilic material is included in the matrix of one or more materials selected from the group consisting of low crystalline carbon and amorphous carbon.
  • the matrix of hydrophilic material may be a structure in which a filler of one or more materials selected from the group consisting of low crystalline carbon and amorphous carbon is included.
  • the matrix forms a phase in which its components are continuous with each other, and the filler forms a phase in which the components thereof are independent of each other, so that the content of the matrix component is necessarily higher than the content of the filler component. no.
  • the content of the at least one material selected from the group consisting of low crystalline carbon and amorphous carbon and the content of the hydrophilic material in the composite coating layer are not particularly limited as long as they are capable of exhibiting the effects (described above) intended in the present invention. .
  • the content of at least one material selected from the group consisting of low crystalline carbon and amorphous carbon may be 10 to 95% by weight, based on the total amount of the composite coating layer, the content of the hydrophilic material of the composite coating layer It may be 5 to 90% by weight based on the total amount.
  • the amount (coating amount) of the composite coating layer is preferably 0.5 to 20% by weight based on the total weight of the negative electrode active material. If the amount of the composite coating layer is too small or the thickness is too thin, it may be difficult to expect the effect of forming the composite coating layer, on the contrary, if the amount of the composite coating layer is too large or too thick, forming the desired core-composite coating layer structure This is undesirable because it can be difficult and can lead to capacity degradation.
  • the present invention also provides a negative electrode mixture composed of the negative electrode active material.
  • the negative electrode mixture according to the present invention contains a binder in the range of 1 to 20% by weight based on the total weight of the copolymer, and may optionally include a conductive material in the range of 0 to 20% by weight.
  • binder examples include polytetrafluoroethylene (PTFE), polyvinylidene fluoride (PVdF), cellulose, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose Rhodes, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, ethylene-propylene-diene terpolymer (EPDM), sulfonated EPDM, styrene butylene rubber, fluorine rubber, various copolymers, high polymer polymerized poly Vinyl alcohol, and the like.
  • PTFE polytetrafluoroethylene
  • PVdF polyvinylidene fluoride
  • CMC carboxymethyl cellulose
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM ethylene-propylene-diene terpolymer
  • EPDM s
  • the conductive material is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • graphite Carbon blacks such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black and summer black
  • Conductive fibers such as carbon fibers and metal fibers
  • Metal powders such as carbon fluoride powder, aluminum powder and nickel powder
  • Conductive whiskeys such as zinc oxide and potassium titanate
  • Conductive metal oxides such as titanium oxide
  • Conductive materials such as polyphenylene derivatives and the like can be used.
  • Specific examples of commercially available conductive materials include Chevron Chemical Company, Denka Singapore Private Limited, Gulf Oil Company, Ketjenblack and EC, which are acetylene black series. Family (Armak Company), Vulcan XC-72 (manufactured by Cabot Company) and Super P (manufactured by Timcal).
  • a filler may optionally be added as a component that inhibits expansion of the negative electrode.
  • a filler is not particularly limited as long as it is a fibrous material without causing chemical change in the battery.
  • the filler include olefinic polymers such as polyethylene and polypropylene; Fibrous materials, such as glass fiber and carbon fiber, are used.
  • viscosity modifiers such as viscosity modifiers, adhesion promoters, and the like may optionally be further included or in combination of two or more.
  • the viscosity modifier is a component for adjusting the viscosity of the electrode mixture to facilitate the mixing process of the electrode mixture and the coating process on the current collector thereof, it may be added up to 30% by weight based on the total weight of the negative electrode mixture.
  • examples of such viscosity modifiers include, but are not limited to, carboxymethyl cellulose, polyvinylidene fluoride, and the like.
  • the solvent described above can serve as a viscosity modifier.
  • the adhesion promoter is an auxiliary component added to improve the adhesion of the active material to the current collector, it may be added in less than 10% by weight compared to the binder, for example, oxalic acid (oxalic acid), adipic acid (adipic acid), Formic acid, acrylic acid derivatives, itaconic acid derivatives, and the like.
  • the present invention also provides a negative electrode for a secondary battery in which the negative electrode mixture is coated on a current collector.
  • the negative electrode may be prepared by adding a negative electrode material including a negative electrode active material and a binder to a solvent such as NMP to prepare a slurry, coating the same on a current collector, and drying and compressing the negative electrode material.
  • a solvent such as NMP
  • the negative electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
  • a negative electrode current collector is not particularly limited as long as it has conductivity without causing chemical change in the battery.
  • the surface of copper, stainless steel, aluminum, nickel, titanium, calcined carbon, copper or stainless steel Surface-treated with carbon, nickel, titanium, silver, and the like, aluminum-cadmium alloy, and the like can be used.
  • the current collector may form fine irregularities on its surface to increase the adhesion of the negative electrode active material, and may be in various forms such as a film, a sheet, a foil, a net, a porous body, a foam, and a nonwoven fabric.
  • the present invention also provides a secondary battery comprising the negative electrode, which may be preferably a lithium secondary battery.
  • the lithium secondary battery has a structure in which a lithium salt-containing non-aqueous electrolyte is impregnated into an electrode assembly having a separator interposed between a positive electrode and a negative electrode.
  • the positive electrode may be manufactured by coating, drying, and applying a positive electrode active material on a positive electrode current collector, and other components described above with respect to the structure of the negative electrode, such as a binder and a conductive material, may optionally be further included.
  • the positive electrode current collector is generally made to a thickness of 3 to 500 ⁇ m.
  • a positive electrode current collector is not particularly limited as long as it has high conductivity without causing chemical changes in the battery.
  • the surface of stainless steel, aluminum, nickel, titanium, calcined carbon, or aluminum or stainless steel Surface treated with carbon, nickel, titanium, silver, or the like can be used.
  • the positive electrode current collector may increase the adhesion of the positive electrode active material by forming minute unevenness on the surface thereof, as in the negative electrode current collector, and may be used in various forms such as film, sheet, foil, net, porous body, foam, and nonwoven fabric. Form is possible.
  • the cathode active material is a material capable of causing an electrochemical reaction, and is a lithium transition metal oxide, and includes two or more transition metals, for example, lithium cobalt oxide (LiCoO 2 ) and lithium substituted with one or more transition metals.
  • LiCoO 2 lithium cobalt oxide
  • the binder, the conductive material and the components added as necessary are the same as those described for the negative electrode.
  • the separator is interposed between the anode and the cathode, an insulating thin film having high ion permeability and mechanical strength is used.
  • the pore diameter of the separator is generally from 0.01 to 10 ⁇ m ⁇ m, thickness is generally 5 ⁇ 300 ⁇ m.
  • a separator for example, a sheet, a nonwoven fabric, or the like made of an olefin polymer such as polypropylene having chemical resistance and hydrophobicity, glass fiber or polyethylene, or the like is used.
  • a gel polymer electrolyte may be coated on the separator to increase battery stability.
  • Representative of such gel polymers are polyethylene oxide, polyvinylidene fluoride, polyacrylonitrile and the like.
  • the solid electrolyte may also serve as a separator.
  • the lithium salt-containing non-aqueous electrolyte is composed of an organic solvent electrolyte and a lithium salt.
  • N-methyl- 2-pyrrolidinone a propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, ethylmethyl carbonate, Gamma-butylo lactone, 1,2-dimethoxy ethane, 1,2-diethoxy ethane, tetrahydroxy franc, 2-methyl tetrahydrofuran, dimethylsulfoxide, 1,3-dioxolon, 4 -Methyl-1,3-dioxene, diethyl ether, formamide, dimethylformamide, dioxolon, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphate esters, trimethoxy methane, dioxonone derivatives Aprotic organic solvents such as sulfolane, methyl sulfolane, 1,3-dimethyl-2-imidazolidinone, propylene
  • organic solid electrolyte examples include polyethylene derivatives, polyethylene oxide derivatives, polypropylene oxide derivatives, phosphate ester polymers, polyedgetion lysine, polyester sulfides, polyvinyl alcohols, polyvinylidene fluorides, Polymerizers containing ionic dissociating groups and the like can be used.
  • Examples of the inorganic solid electrolyte include Li 3 N, LiI, Li 5 NI 2 , Li 3 N-LiI-LiOH, LiSiO 4 , LiSiO 4 -LiI-LiOH, Li 2 SiS 3 , Li 4 SiO 4 , Nitrides, halides, sulfates and the like of Li, such as Li 4 SiO 4 -LiI-LiOH, Li 3 PO 4 -Li 2 S-SiS 2 , and the like, may be used.
  • the lithium salt is a good material to be dissolved in the non-aqueous electrolyte, for example, LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 , LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (CF 3 SO 2) 2 NLi, chloroborane lithium, lower aliphatic carboxylic acid lithium, 4 phenyl lithium borate, imide and the like can be used.
  • LiCl, LiBr, LiI, LiClO 4 , LiBF 4 , LiB 10 Cl 10 LiPF 6 , LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6, LiSbF 6, LiAlCl 4, CH 3 SO 3 Li, CF 3 SO 3 Li, LiSCN, LiC (CF 3 SO 2) 3, (
  • pyridine triethyl phosphite, triethanolamine, cyclic ether, ethylene diamine, n-glyme, hexaphosphate triamide, nitro Benzene derivatives, sulfur, quinone imine dyes, N-substituted oxazolidinones, N, N-substituted imidazolidines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxy ethanol, aluminum trichloride and the like may be added. .
  • a halogen-containing solvent such as carbon tetrachloride or ethylene trifluoride may be further included, and carbon dioxide gas may be further included to improve high temperature storage characteristics, and FEC (Fluoro-Ethylene) may be further included. Carbonate), PRS (Propene sultone) may be further included.
  • lithium salts such as LiPF 6 , LiClO 4 , LiBF 4 , LiN (SO 2 CF 3 ) 2, and the like, may be prepared by cyclic carbonate of EC or PC as a highly dielectric solvent and DEC, DMC or EMC as a low viscosity solvent.
  • Lithium salt-containing non-aqueous electrolyte can be prepared by adding to a mixed solvent of linear carbonate.
  • the present invention also provides a medium-large battery pack using the secondary battery as a unit cell.
  • the negative electrode containing the hydrophilic material as in the present invention is very preferable because it can greatly shorten the time of this impregnation process.
  • Preferred examples of such battery packs include, but are not limited to, lithium ion secondary battery packs for automobiles or power storage.
  • the graphite-based negative electrode active material coated with the carbon / aluminum oxide composite was prepared by forming a composite with aluminum oxide and coating the graphite surface while the pitch softened and carbonized during the heat treatment.
  • a coin-type half cell was prepared after preparing an anode active material in the same manner as in Example 1 except that magnesium oxide (MgO) having an average particle diameter of about 100 nm was used instead of aluminum oxide (Al 2 O 3 ).
  • magnesium oxide MgO
  • Al 2 O 3 aluminum oxide
  • a negative electrode active material was prepared in the same manner as in Example 1 except that the mixing ratio of the graphite, pitch, and aluminum oxide was 90: 1: 1, and then coin-shaped half cells were prepared.
  • the content of aluminum oxide is more than 90% based on the entire carbon and aluminum oxide.
  • Electrolytic solution impregnation characteristics were evaluated using the electrodes prepared according to Examples 1 and 2 and Comparative Examples 1 and 2. After the electrode was rolled to have a porosity of 23%, 1 microliter ( ⁇ l) of an electrolyte solution containing 1 M of LiPF 6 dissolved in a carbonate solvent on the surface of the electrode was measured and the time until complete penetration was measured. It is shown in Table 1 below.
  • the electrolyte solution impregnation time is coated only with carbon as in Comparative Example 1 It can be seen that it is much shorter than the electrode using the negative electrode active material. This is because a polar electrolyte solution can quickly penetrate between particles by coating a hydrophilic material on the surface of the negative electrode active material.
  • Charge and discharge characteristics were evaluated using coin type half cells prepared according to Examples 1 and 2, and Comparative Examples 1 and 2. Specifically, after charging CC mode to 5 mV at a current density of 0.1C at the time of charging, charging was maintained at 5 mV constant in CV mode to complete charging when the current density became 0.01C. When discharged, the discharge was completed in CC mode up to 1.5V at a current density of 0.1C to obtain the first cycle charge and discharge capacity and efficiency. Thereafter, only the current density was changed to 0.5C, and the rest was repeated 50 times under the same conditions as above, and the results are shown in Table 2 below.
  • the negative electrode active material according to the present invention has a characteristic core / composite coating layer structure, which greatly improves the manufacturing process of the battery, minimizes the decrease in the electrical conductivity, and significantly reduces the collapse of the SEI film and consequently the battery life. There is an effect that can be suppressed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Power Engineering (AREA)
  • Transportation (AREA)
  • Mechanical Engineering (AREA)
  • Composite Materials (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

La présente invention concerne un matériau de cathode pour une batterie secondaire capable d'occlure et d'émettre des ions, comprenant : un noyau comprenant un matériau à base de carbone cristallin ; et une couche de revêtement composite comprenant au moins une substance choisie dans le groupe constitué par du carbone faiblement cristallin et du carbone amorphe, et une substance hydrophile. Dans le matériau cathode, le revêtement composite est composé d'une structure comprenant : une matrice composée d'au moins une substance choisie dans le groupe constitué par des substances de carbone faiblement cristallin et de carbone amorphe, et présentant comme ingrédient une substance choisie dans un groupe de substances hydrophiles ; et une charge composée du reste des ingrédients de la matrice. La présente invention concerne également une batterie secondaire comprenant le matériau de cathode.
PCT/KR2011/009169 2010-12-08 2011-11-29 Matériau de cathode et batterie secondaire utilisant ledit matériau Ceased WO2012077929A2 (fr)

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Application Number Priority Date Filing Date Title
EP11847200.0A EP2650953B1 (fr) 2010-12-08 2011-11-29 Matériau de cathode et batterie secondaire utilisant ledit matériau
PL11847200T PL2650953T3 (pl) 2010-12-08 2011-11-29 Materiał katody oraz akumulator, w którym się go stosuje
CN201180058590.8A CN103250284B (zh) 2010-12-08 2011-11-29 负极活性材料和包含所述负极活性材料的二次电池
US13/904,588 US8974962B2 (en) 2010-12-08 2013-05-29 Anode active material and secondary battery comprising the same

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KR20100124809 2010-12-08
KR10-2010-0124809 2010-12-08

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US13/904,588 Continuation US8974962B2 (en) 2010-12-08 2013-05-29 Anode active material and secondary battery comprising the same

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WO2012077929A2 true WO2012077929A2 (fr) 2012-06-14
WO2012077929A3 WO2012077929A3 (fr) 2012-10-04

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EP (1) EP2650953B1 (fr)
KR (1) KR101334594B1 (fr)
CN (1) CN103250284B (fr)
PL (1) PL2650953T3 (fr)
WO (1) WO2012077929A2 (fr)

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Also Published As

Publication number Publication date
CN103250284B (zh) 2015-12-02
KR101334594B1 (ko) 2013-11-29
CN103250284A (zh) 2013-08-14
WO2012077929A3 (fr) 2012-10-04
EP2650953A4 (fr) 2017-01-11
EP2650953B1 (fr) 2019-08-28
PL2650953T3 (pl) 2019-12-31
US20130260237A1 (en) 2013-10-03
EP2650953A2 (fr) 2013-10-16
US8974962B2 (en) 2015-03-10
KR20120064023A (ko) 2012-06-18

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